WO2020076620A1 - Composition d'organopolysiloxane à double durcissement - Google Patents

Composition d'organopolysiloxane à double durcissement Download PDF

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WO2020076620A1
WO2020076620A1 PCT/US2019/054620 US2019054620W WO2020076620A1 WO 2020076620 A1 WO2020076620 A1 WO 2020076620A1 US 2019054620 W US2019054620 W US 2019054620W WO 2020076620 A1 WO2020076620 A1 WO 2020076620A1
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groups
mass
organopolysiloxane
component
parts
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PCT/US2019/054620
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English (en)
Inventor
Junying Liu
Xianghuai WANG
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Dow Silicones Corporation
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Priority to EP19870305.0A priority Critical patent/EP3864072A4/fr
Priority to CN201980057742.9A priority patent/CN112638992B/zh
Priority to JP2021513781A priority patent/JP7442508B2/ja
Priority to KR1020217013354A priority patent/KR20210057195A/ko
Priority to US17/282,944 priority patent/US20210388208A1/en
Publication of WO2020076620A1 publication Critical patent/WO2020076620A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to dual curable organopolysiloxane compositions which are capable of cross-linking when subjected to radiation in the ultraviolet (“UV”) region of the electromagnetic spectrum, and subjected to moisture
  • Curable organopolysiloxane compositions exist in various forms and their characteristics may be modified to impart specific characteristics such as cure chemistry, viscosity, polymer type and purity. They can be formulated into one-part or two-part systems and a particular curable organopolysiloxane composition can be engineered to be cured by more than one mechanism. Moisture-curing mechanisms, heat-curing mechanisms, and photo-initiated curing mechanisms are among those mechanisms used to initiate cure, i.e., cross-linking of reactive organopolysiloxanes.
  • reactive organopolysiloxanes can be cured by heat in the presence of a peroxide, or they can be cured by heat in the presence of a silicon hydride-containing (SiH) compound and a metallic hydrosilylation catalyst, such as a platinum catalyst.
  • moisture curable organopolysiloxane compositions are manufactured by endcapping a,w-silanol terminated organopolysiloxanes with various crosslinkers such as alkoxysilanes, oximinosilanes, acetoxysilanes, aminosilanes, and other silanes with hydrolyzable groups attached to the silicon atom(s) thereof.
  • the resulting curable organopolysiloxane compositions are stored in moisture impermeable containers.
  • the curable organopolysiloxane compositions are extruded or otherwise applied and exposed to ambient conditions for curing.
  • the moisture in the air then will hydrolyze the hydrolyzable groups (such as alkoxy, oximino, acetoxy, and amino) on the silicon atom(s) to form silanol, either with or without inclusion of a catalyst.
  • the resulting silanol can then further react with remaining unhydrolyzed groups in a condensation reaction, to form a siloxane linkage resulting in the cure of the curable organopolysiloxane composition.
  • these materials when cured are very reliable and possess superior properties as coatings, the moisture cure tends to be slow. Cure times of 24 hours or more may often be needed before a full cure can be achieved. Such cure times limit through-put in the manufacture of coated components, since full cure of the coated components may be needed before the components can be used in the next step of the manufacture process.
  • a third curing mode ultraviolet light curing
  • the curing is relatively fast, with the cured elastomer showing better adhesion to the substrates.
  • a secondary cure mode usually moisture cure can be further incorporated.
  • UV-curable organopolysiloxane compositions can be achieved by either a thiol-ene cure or by an acrylate cure.
  • a thiol-ene cure a mercapto (-SH) functional organopolysiloxane is reacted with an alkenyl group-containing organopolysiloxane. The cure is fast and the surface dry to the touch upon the completion of the cure.
  • Patent Document 1 Dual curable organopolysiloxane compositions using UV light and moisture curing mechanisms are disclosed in Patent Document 1 .
  • This reference discloses compositions particularly useful for conformal coatings in electronic applications where the substrate has shadow areas which are not readily accessible to direct UV light and require moisture cure for cross-linking of those areas.
  • a condensation catalyst such as an organotitanate or organotin is present. Without the condensation catalyst, moisture cure does not ordinarily take place with any degree of certainty or in any predictable time frame. Thus, as a practical matter, without the condensation catalyst, the moisture curing aspect of these compositions would not be practical for commercial use.
  • Patent Document 1 U.S. Pat. No. 4,528,081
  • An object of the present invention is to provide a dual curable organopolysiloxane composition which has the ability to both photo-cure and cure through exposure to moisture, and which exhibits excellent curability and long-term storage stability.
  • composition comprising:
  • component (B) a second organopolysiloxane having at least one alkenyl group and at least one silicon atom-bonded alkoxy group per molecule, in an amount such that the amount of the mercapto groups in component (A) is in the range of from about 0.1 to about 10 moles per 1 mole of the total alkenyl groups in components (B) and (C);
  • (C) an organopolysiloxane having at least two alkenyl groups per molecule and free of a silicon atom-bonded alkoxy group, in an amount of from about 0 to about 80 mass% of the total mass of components (B) and (C);
  • component (A) is an organopolysiloxane comprising at least two siloxane units represented by the following general formula:
  • Ft 1 represents a divalent hydrocarbon group with 1 to 8 carbons
  • Ft 2 represents an alkyl group, an aryl group, a hydrogen atom, a hydroxyl group or an alkoxy group
  • x is 0, 1 or 2.
  • Component (A) may have the mercapto (-SH) groups in the range of from about 0.5 to about 15.0 mass%.
  • component (B) is an organopolysiloxane produced by a hydrosilation reaction of (B-1 ) an organopolysiloxane having at least two alkenyl groups per molecule and (B-2) an organosilicon compound having one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded alkoxy group per molecule.
  • component (C) is 4,4'-bis(dimethylamino)benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1 ,2-diphenylethan-1 -one, 1 -hydroxycyclohexyl- phenyl-ketone, 2-hydroxy-2-methyl-1 -phenyl-propan-1 -one, 2-methyl-1 -[4-
  • component (D) is an organo-metal catalyst selected from a group consisting of titanium compounds, zirconium compounds, and tin compounds.
  • component (E) is an epoxy functional organosilicon compound.
  • the epoxy functional silicon compound can be 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 3-glycidoxypropyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, 5,6-epoxyhexyl trimethoxysilane, 5,6-epoxyhexyl triethoxysilane, or 8-glycidoxyoctyl trimethoxysilane, or combinations thereof.
  • the composition results from both a UV-radiation cure mechanism and a moisture cure mechanism.
  • the composition is for use as a potting (or a pottant), a coating, an adhesive, or an encapsulation.
  • the dual curable organopolysiloxane composition according to this disclosure generally has the ability to both photo-cure and cure through exposure to moisture, and exhibits good to excellent curability and long-term storage stability.
  • Figure 1 is a photo of the cross-cut test result of Practical Example 1 .
  • Figure 2 is a photo of the cross-cut test result of Practical Example 2.
  • Figure 3 is a photo of the cross-cut test result of Comparative Example 1 .
  • Such minor variations may be in the order of ⁇ 0-25, ⁇ 0-10, ⁇ 0-5, or ⁇ 0-2.5, % of the numerical values. Further, the term“about” applies to both numerical values when associated with a range of values. Moreover, the term“about” may apply to numerical values even when not explicitly stated.
  • a hyphen or dash in a range of values is“to” or “through”; a“>” is“above” or“greater-than”; a“>” is“at least” or“greater-than or equal to”; a “ ⁇ ” is“below” or“less-than”; and a“£” is“at most” or“less-than or equal to.”
  • a“>” is“above” or“greater-than”
  • a“>” is“at least” or“greater-than or equal to”
  • a “ ⁇ ” is“below” or“less-than”
  • a“£” is“at most” or“less-than or equal to.”
  • a range“of from 0.1 to 0.9” may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims.
  • a range“at least,”“greater than,”“less than,”“no more than,” and the like it is to be understood that such language includes subranges and/or an upper or lower limit.
  • a range of “at least 10” inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims.
  • an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims.
  • a range“of from 1 to 9” includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1 , which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.
  • Component (A) is an organopolysiloxane having at least two mercapto (-SH) functional groups per molecule.
  • mercapto functional groups include mercaptoalkyl groups such as 3-mercaptopropyl groups, 4-mercaptobutyl groups, and 6- mercaptohexyl groups.
  • examples of groups other than mercapto functional groups that are bonded to the silicon atom in component (A) include: alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like; aryl groups with 6 to 12 carbons such as phenyl groups, tolyl groups, xylyl groups, and the like; aralkyl groups with 7 to 12 carbons such as benzyl groups, phenetyl groups, and the like; halogen substituted alkyl groups with 1 to 12 carbons such as 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, and the like.
  • methyl groups are present.
  • the silicon atom in component (B) may be bonded to a small amount of hydrogen atoms, hydroxyl groups or alkoxy groups such as methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, sec-butoxy groups, tert- butoxy groups and the like.
  • component (A) is an organopolysiloxane comprising at least two siloxane units of the following general formula:
  • Ft 1 represents a divalent hydrocarbon group.
  • divalent hydrocarbon groups include: alkylene groups with 1 to 8 carbons such as methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, heptylene groups, and octylene groups.
  • propylene groups are present.
  • Ft 2 represents an alkyl group, an aryl group, a hydrogen atom, a hydroxyl group or an alkoxy group.
  • Ft 2 include: alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like; aryl groups with 6 to 12 carbons such as phenyl groups, tolyl groups, xylyl groups, and the like; alkoxy groups with 1 to 6 carbons such as methoxy groups, ethoxy groups, propoxy groups, and the like. In certain embodiments, from the perspective of economics and heat resistance, methyl groups are present. [0034] In the formula, "x" is 0, 1 or 2. When “x" is 0, the siloxane unit is a siloxane unit is
  • siloxane unit is a D unit represented by the following general formula:
  • siloxane unit is an M unit represented by the following general formula:
  • Such component (A) may have mercapto (-SH) groups in the range of from about 0.5 to about 15.0 mass%, optionally of from about 0.5 to about 10.0 mass%, optionally of from about 1 .0 to about 15.0 mass%, optionally of from about 1 .0 to about 10.0 mass%, optionally of from about 1 .0 to about 5.0 mass%, or optionally of from about 1 .0 to about 4.0 mass%, of the component.
  • mercapto (-SH) groups in the range of from about 0.5 to about 15.0 mass%, optionally of from about 0.5 to about 10.0 mass%, optionally of from about 1 .0 to about 15.0 mass%, optionally of from about 1 .0 to about 10.0 mass%, optionally of from about 1 .0 to about 5.0 mass%, or optionally of from about 1 .0 to about 4.0 mass%, of the component.
  • mercapto (-SH) groups in the range of from about 0.5 to about 15.0 mass%, optionally of from about
  • Component (B) is an organopolysiloxane having at least one alkenyl group and at least one silicon atom-bonded alkoxy group per molecule.
  • alkenyl group include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups.
  • at least one of vinyl groups, allyl groups, hexenyl groups, and octenyl groups are present.
  • component (B) may have at least two alkenyl groups per molecule.
  • alkoxy group examples include methoxy groups, ethoxy groups, propoxy groups, and butoxy groups. In certain embodiments, from the perspective of economics and curability, at least one of methoxy groups and ethoxy groups are present. In particular, in view of the excellent curablility of the composition by moisture, component (B) may have at least two silicon atom-bonded alkoxy groups per molecule.
  • examples of groups other than alkenyl groups and alkoxy groups that are bonded to the silicon atom in component (B) include: alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like; aryl groups with 6 to 12 carbons such as phenyl groups, tolyl groups, xylyl groups, and the like; aralkyl groups with 7 to 12 carbons such as benzyl groups, phenetyl groups, and the like; halogen substituted alkyl groups with 1 to 12 carbons such as 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, and the like.
  • alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups,
  • Component (B) may be produced by a hydrosilation reaction of (B-1 ) an organopolysiloxane having at least two alkenyl groups per molecule and (B-2) an organosilicon compound having one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded alkoxy group per molecule.
  • Raw material (B-1 ) is an organopolysiloxane having at least two alkenyl groups per molecule.
  • alkenyl group include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups.
  • at least one of vinyl groups, allyl groups, hexenyl groups, and octenyl groups are present.
  • Examples of groups other than alkenyl groups that are bonded to the silicon atom in raw material (B-1 ) include: alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like; aryl groups with 6 to 12 carbons such as phenyl groups, tolyl groups, xylyl groups, and the like; aralkyl groups with 7 to 12 carbons such as benzyl groups, phenetyl groups, and the like; halogen substituted alkyl groups with 1 to 12 carbons such as 3-chloropropyl groups, 3,3,3- trifluoropropyl groups, and the like.
  • alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propy
  • Raw material (B-2) is an organosilicon compound having one silicon atom-bonded hydrogen atom and at least one silicon atom-bonded alkoxy group per molecule.
  • alkoxy group include alkoxy groups with 1 to 6 carbons such as methoxy groups, ethoxy groups, propoxy groups, and butoxy groups. In certain embodiments, methoxy groups are present.
  • raw material (B-2) is an organosilicon compound having a trialkoxysilyl group or a dialkoxysilyl group.
  • Examples of raw material (B-2) include the following compounds. Note that, in the formulas, "Me” and “Et” respectively indicate a methyl group and an ethyl group.
  • the added amount of raw material (B-2) is not limited, but in various embodiments it is in an amount such that the amount of the silicon atom-bonded hydrogen atoms in raw material (B-2) is from 0.1 to 0.9 mol, optionally from 0.2 to 0.8 mol, or optionally from 0.3 to 0.7 mol, per 1 mol of the alkenyl groups in raw material (B-1 ). This is because, when the added amount of component (B-2) is within the range described above, an organopolysiloxane that practically has at least one alkenyl group and at least one silicon atom-bonded alkoxy group per molecule can be obtained.
  • the hydrosilation reaction is enhanced by heating in the presence of a hydrosilation catalyst.
  • a hydrosilation catalyst include platinum-based catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, alkenylsiloxane complexes of platinum, platinum black, and platinum-supported silica.
  • the content of component (B) in the composition is such that the amount of the mercapto (-SH) groups in component (A) is in the range of from about 0.1 to about 10 moles, optionally of from about 0.5 to about 5 moles, or optionally of from about 0.5 to about 1 .5 moles, per 1 mole of the alkenyl groups in component (B) and (C). This is because if the amount of component (B) is within the aforementioned range, it will lead to sufficient cure to provide good mechnical properties.
  • Component (C) is an arbitrary or optional component, and is an organopolysiloxane having at least two alkenyl groups per molecule and free of a silicon atom-bonded alkoxy group.
  • alkenyl group include vinyl groups, allyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, decenyl groups, undecenyl groups, and dodecenyl groups.
  • at least one of vinyl groups, allyl groups, hexenyl groups, and octenyl groups are present.
  • Examples of groups other than alkenyl groups that are bonded to the silicon atom in component (C) include: alkyl groups with 1 to 12 carbons such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, and the like; aryl groups with 6 to 12 carbons such as phenyl groups, tolyl groups, xylyl groups, and the like; aralkyl groups with 7 to 12 carbons such as benzyl groups, phenetyl groups, and the like; halogen substituted alkyl groups with 1 to 12 carbons such as 3-chloropropyl groups, 3,3,3- trifluoropropyl groups, and the like. In certain embodiments, from the perspective of economics and heat resistance, methyl groups are present.
  • component (C) is present in an amount of from about in an amount of from about 0 to about 80 mass%, optionally of from about 10 to about 80 mass%, optionally of from about 20 to about 80 mass%, optionally of from 30 to about 80 mass%, or optionally of from about 40 to about 80 mass%, of the total mass of components (B) and (C). This is because if the amount of component (C) is within the aforementioned range, it will lead to sufficient cure to provide good mechnical properties.
  • Component (D) is a photo-initiator to enhance photo-cure of the composition.
  • Component (D) may be selected from any known free radical type photo-initiator effective for promoting crosslinking reactions.
  • Examples of component (D) include diethoxyacetophenone (DEAP), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, diethoxyxanthone, chloro-thioxanthone, azo-bisisobutyronitrile, N-methyl diethanolaminebenzophenone 4,4'-bis(dimethylamino)benzophenone, diethoxyacetophenone, 2,2-dimethoxy-1 ,2-diphenylethan-1 -one, 1 -hydroxycyclohexyl- phenyl-ketone, 2-hydroxy-2-methyl-1 -phenylpropan-1 -one, 2-methyl-1 -[4-
  • component (D) is in effective amount for photo-cure.
  • component (D) is present in an amount of from about 0.01 to about 5 parts by mass, optionally of from about 0.1 to about 5 parts by mass, or optionally of from about 0.1 to about 3 parts by mass, per 100 parts by the total mass of components (A) to (F). This is because if the amount of component (D) is above the lower limit of the range, the composition obtained will sufficiently cure by UV light; however, if, on the other hand, the amount is below the upper limit of the aforementioned range, the mechanical properties of the cured product obtained will be enhanced.
  • Component (E) is a condensation catalyst to enhance moisture cure of the composition.
  • component (E) include organo-metal catalysts including titanium compounds such as tetra(isopropoxy)titanium, tetra(n-butoxy)titanium, tetra(t- butoxy)titanium, di(isopropoxy)bis(ethylacetoacetate)titanium, di(isopropoxy)bis(methylacetoacetate)titanium, di(isopropoxy)bis(acetylacetonate)titanium, and the like; zirconium compounds such as tetra(isopropoxy)zirconium, tetra(n- butoxy)zirconium, tetra(t-butoxy)zirconium, di(isopropoxy)bis(ethylacetoacetate)zirconium, di(isopropoxy)bis(methylacetoacetate)zirconium,
  • organo-metal catalysts including
  • component (E) is in effective amount for moisture cure.
  • component (E) is present in an amount of from about 0.01 to about 10 parts by mass, optionally of from about 0.05 to about 10 parts by mass, or optionally of from about 0.05 to about 5 parts by mass, per 100 parts by the total mass of components (A) to (F). This is because if the amount of component (E) is above the lower limit of the range, the composition obtained will sufficiently cure by moisture; and if the amount is below the upper limit of the aforementioned range, surface cure rate of the resulting composition is improved.
  • Component (F) is an epoxy functional compound to enhance long-term stability of the composition.
  • component (F) include epoxy functional organosilicon compounds such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3- glycidoxypropyl methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 2- (3,4-epoxycyclohexyl)ethyl methyldimethoxysilane, 3,4-epoxybutyl trimethoxysilane, 3,4- epoxybutyl methyldimethoxysilane, 5,6-epoxyhexyl trimethoxysilane, 5,6-epoxyhexyl triethoxysilane, 8-glycidoxyoctyl trimethoxysilane, and the like; and epoxy functional non silicon compounds such as methyl glycidyl trime
  • component (F) is in effective amount for long term storage stability.
  • component (F) is present in an amount of from about 0.01 to about 10 parts by mass, optionally of from about 0.05 to about 10 parts by mass, or optionally of from about 0.05 to about 5 parts by mass, per 100 parts by mass of the sum of components (A) to (F). This is because if the amount of component (F) is above the lower limit of the range, the composition obtained will have sufficient long term storage stability; and if the amount is below the upper limit of the aforementioned range, mechanical properties of the cured product obtained will be enhanced.
  • the composition may also contain one or more other additives so long as they do not interfere with the curing mechanisms.
  • additives such as fillers, adhesion promoters, resins, pigments, moisture scavengers, fluorescent dye, inhibitors and the like may be included.
  • Fillers such as fumed silica or quartz are contemplated. Fillers may be present in amounts up to about 30 mass%, such as from about 4 to about 20 mass% of the total mass of components (A) to (F). [0058] Inhibitors may be present in amounts up to about 5% by weight, such as from about 0.001 to about 1 mass% of the total mass of components (A) to (F). The particular amount of inhibitor should be balanced in a given composition to produce or improve stability of the composition. Such amounts can be determined via routine experimentation.
  • Adhesion promoters may be present in amounts up to about 5 mass%, such as from about 0.5 mass% of the total mass of components (A) to (F).
  • the composition may be prepared by mixing together the respective components to obtain a substantially homogenous or uniformly blended material and stored in containers which are non-transmissive to UV light and moisture.
  • a single package system is utilized, but two-part package systems may be used if desired. Whereas single package products are ready-for-use upon being dispersed, two-part systems generally require mixing of the dispersed parts prior to use.
  • composition may be used as noted above in potting applications and coatings, encapsulations, gels for a variety of substrates including electronic parts and other heat-sensitive materials.
  • Useful UV radiation sources include conventional mercury-vapor lamps designed to emit ultraviolet energy in various ultraviolet wavelength bands, LED curing lamps, etc.
  • useful radiation wavelength ranges include 200 to 400 nm.
  • UV cure is generally effected in the range of 40 milliwatts/cm 2 (“mW/cm 2 ”) to about
  • 300 mW/cm 2 such as in the range of about 70 mW/cm 2 to about 300 mW/cm 2 .
  • Viscosities for all dual curable organopolysiloxane compositions were measured using a Brookfield cone and plate viscometer (model HBDVII+P) with the cone spindle CP- 40.
  • Viscosity of the organopolysiloxanes were measured using a Brookfield DV1 viscometer according to ASTM D 1084 at 23 ⁇ 2 °C.
  • 2841 cm 1 peak in IR is the characteristic band for -OMe;
  • 2582 cm 1 in Raman spectra is the characteristic of -SH group which is normalized to the overtone of the Si-Me deformation band located at 2498 cm 1 ;
  • the dual curable organopolysiloxane compositions were examined by Raman spectroscopy using a Raman microprobe spectrometer (Thermofisher DXR) equipped with a 532 nm diode laser and a 10x objective lens.
  • the Raman spectra were collected with total
  • Dual curable organopolysiloxane compositions were subjected to ultraviolet irradiation using A Colight UV-6 with mercury lamp at UV intensity of 300 mW/cm 2 and a dosage of 2J/cm 2 . After the irradiation, the UV exposure area were cured to tack free. The shadow areas are cured and become tack-free after 24 to 48 hours cure at 22 q C/42%RH. ⁇ Shore A Hardness>
  • Hardness of the cured product as mentioned above was measured by a Shore A durometer (CV-71200 from INST & MFG Co).
  • trimethoxysilyl- and vinyl-functional dimethylpolysiloxane practically has at least one vinyl group and at least one trimethoxysilyl group per molecule, and the content of vinyl groups is 0.6 mass% and the content of trimethoxysilyl groups is 0.8 mass%.
  • a dual curable organopolysiloxane composition was prepared by blending together 16.8 parts by mass of a dimethylsiloxane methyl(3-mercaptopropyl)siloxane copolymer having 3.5 mass% of SH groups and a viscosity of 80 mPa-s; 19.0 parts by mass of an organopolysiloxane consisting of Me 2 ViSiO-
  • a dual curable organopolysiloxane composition was prepared as described in Practical Example 1 except that 1 .0 part by mass of 3-glycidoxypropyl trimethoxysilane was added.
  • a dual curable organopolysiloxane composition was prepared as described in Practical Example 1 except that 2.0 parts by mass of 3-glycidoxypropyl trimethoxysilane was added.
  • a dual curable organopolysiloxane composition was prepared as described in Practical Example 1 except that 3-glycidoxypropyl trimethoxysilane was not added.
  • a dual curable organopolysiloxane composition was prepared by blending together 16.8 parts by mass of a random copolymer of dimethylsiloxane and methyl(3- mercaptopropyl)siloxane having 3.5 mass% of SH groups and a viscosity of 80 mPa-s; 19 parts by mass of an organopolysiloxane consisting of Me 2 ViSiO-
  • the mixture was mixed at 1000 rpm for 20 seconds, and then mixed at 2000 rpm for 30 seconds. Premixed 0.3 parts by mass of 1 -hydroxycyclohexyl-phenyl-ketone; 0.85 parts by mass of methyl trimethoxysilane; and 0.05 parts by mass of butylated hydroxytoluene, 0.5 parts by mass of 3-glycidoxypropyl trimethoxysilane were added. The mixture was mixed at 2000 rpm for 30 seconds. Finally, 0.12 parts by mass of di-isopropoxytitanium bis(ethylacetoacetate) was added in a dental mixer; and the blend was mixed at 2000 rpm for 30 seconds. The sample was then packaged in 30 ml. syringe and deaerated; and then vacuum sealed in an aluminum bag.
  • a dual curable organopolysiloxane composition was prepared by blending together 18.4 parts by mass of a random copolymer of dimethylsiloxane and methyl(3- mercaptopropyl)siloxane having 3.5 mass% of SH groups and a viscosity of 80 mPa-s; 19.0 parts by mass of an organopolysiloxane consisting of Me 2 ViSiO-
  • the mixture was mixed at 1000 rpm for 20 seconds, and then mixed at 2000 rpm for 30 seconds.
  • Premixed 0.3 parts by mass of 1 -hydroxycyclohexyl-phenyl-ketone; 0.85 parts by mass of methyl trimethoxysilane; 0.05 parts by mass of butylated hydroxytoluene, and 0.5 parts by mass of 3-methacryloxypropyl trimethoxysilane were added; the mixture was mixed at 2000 rpm for 30 seconds.
  • 0.12 parts by mass of di-isopropoxytitanium bis(ethylacetoacetate) were added; and the composition was mixed at 2000 rpm for 30 seconds.
  • the sample was then packaged in 30 ml.
  • a dual curable organopolysiloxane composition was prepared by blending together
  • the mixture was mixed at 1000 rpm for 20 seconds, and then mixed at 2000 rpm for 30 seconds. Premixed 2 part by mass of methyl trimethoxysilane; 0.15 parts by mass of butylated hydroxytoluene; and 0.5 parts by mass of 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane were added. The mixture was mixed at 2000 rpm for 30 seconds. Finally, 0.3 parts by mass of 2-hydroxy-2-methyl-1 - phenyl-propan-1 -one and 0.15 parts by mass of di-isopropoxytitanium bis(ethylacetoacetate) were added; and the composition was mixed at 2000 rpm for 30 seconds. The sample was then packaged in 30 ml syringe and deaerated; and then vacuum sealed in an aluminum bag. Comparative Example 4>
  • a dual curable organopolysiloxane composition was prepared as described in Practical Example 5 except without 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane.
  • the dual curable organopolysiloxane compositions in Practical Example 5 and Comparative Example 4 were subjected to an accelerated aging test at 55 °C for 28 days.
  • the viscosity of the composition was measured before and after aging and the results are shown in Table 4.
  • the dual curable organopolysiloxane composition of this disclosure is advantageously used as a conformal coating of an electric/electronic apparatus, because it cures at room temperature subjected to UV radiation and by contact with moisture in air and forms a cured product that exhibits good to excellent adhesion to the substrate contacted during curing, and good to excellent mechanical properties such as a breaking stress and/or elongation.

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Abstract

La présente invention concerne une composition d'organopolysiloxane à double durcissement. La composition comporte : (A) un premier organopolysiloxane ayant au moins deux groupes fonctionnels mercapto (-SH) par molécule et exempt d'un groupe alcényle ; (B) un second organopolysiloxane ayant au moins un groupe alcényle et au moins un groupe alcoxy lié à un atome de silicium par molécule ; (C) éventuellement un organopolysiloxane ayant au moins deux groupes alcényle par molécule et exempt de groupe alcoxy lié à un atome de silicium ; (D) un photo-initiateur ; (E) un catalyseur de condensation ; (F) un composé fonctionnel époxy. La composition possède la capacité à la fois de photo-durcir et de durcir par exposition à l'humidité, ainsi que de bonnes à excellentes caractéristiques en termes d'aptitude au durcissement et de stabilité au stockage à long terme.
PCT/US2019/054620 2018-10-08 2019-10-04 Composition d'organopolysiloxane à double durcissement WO2020076620A1 (fr)

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EP19870305.0A EP3864072A4 (fr) 2018-10-08 2019-10-04 Composition d'organopolysiloxane à double durcissement
CN201980057742.9A CN112638992B (zh) 2018-10-08 2019-10-04 可双重固化有机聚硅氧烷组合物
JP2021513781A JP7442508B2 (ja) 2018-10-08 2019-10-04 二重硬化性オルガノポリシロキサン組成物
KR1020217013354A KR20210057195A (ko) 2018-10-08 2019-10-04 이중 경화성 유기폴리실록산 조성물
US17/282,944 US20210388208A1 (en) 2018-10-08 2019-10-04 Dual curable organopolysiloxane composition

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WO2022051207A1 (fr) * 2020-09-01 2022-03-10 Dow Silicones Corporation Composition à double durcissement par uv/humidité présentant une adhérence de substrat améliorée
WO2022220930A1 (fr) 2021-04-12 2022-10-20 Dow Silicones Corporation Composition d'organopolysiloxanes à double durcissement présentant de la stabilité pendant sa conservation
WO2023107198A1 (fr) * 2021-12-08 2023-06-15 Dow Silicones Corporation Silicones à double durcissement à durcissement rapide à basse température
WO2024030296A1 (fr) * 2022-07-31 2024-02-08 Dow Silicones Corporation Composition durcissable et procédé de formation d'un produit durci

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WO2023244898A1 (fr) * 2022-06-15 2023-12-21 Dow Global Technologies Llc Procédé de préparation de copolymères de polyorganosiloxane
KR102619618B1 (ko) * 2022-12-22 2024-01-04 모멘티브 퍼포먼스 머티리얼즈 인크. 실리콘계 조성물 및 이의 경화물
WO2024136390A1 (fr) * 2022-12-23 2024-06-27 Dow Silicones Corporation Composition d'organopolysiloxanes à double durcissement présentant de la stabilité pendant sa conservation

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WO2022051207A1 (fr) * 2020-09-01 2022-03-10 Dow Silicones Corporation Composition à double durcissement par uv/humidité présentant une adhérence de substrat améliorée
KR20230044559A (ko) * 2020-09-01 2023-04-04 다우 실리콘즈 코포레이션 향상된 기재 접착력을 갖는 uv/수분 이중 경화 조성물
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WO2022220930A1 (fr) 2021-04-12 2022-10-20 Dow Silicones Corporation Composition d'organopolysiloxanes à double durcissement présentant de la stabilité pendant sa conservation
WO2023107198A1 (fr) * 2021-12-08 2023-06-15 Dow Silicones Corporation Silicones à double durcissement à durcissement rapide à basse température
WO2024030296A1 (fr) * 2022-07-31 2024-02-08 Dow Silicones Corporation Composition durcissable et procédé de formation d'un produit durci

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JP7442508B2 (ja) 2024-03-04
TW202024241A (zh) 2020-07-01
CN112638992A (zh) 2021-04-09
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KR20210057195A (ko) 2021-05-20
US20210388208A1 (en) 2021-12-16

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